Treatment of hydrocarbons



Patented July 18, 1944 TREATMENT OF HYDROCARBONS Louis Schmerling, Chicago, Ill.,.assignor to Universal Oil Products Company, corporation of Delaware Application May 9, 1942,

No Drawing.

Chicago, 111., a

Serial N 0. 442,383

21 Claims.

This'invention relates to the condensation of isoparaffins with halo-olefins in the presence of metal halide catalysts of the Friedel-Crafts type. More specifically, the process is concerned with a method of reacting isoparaiiinic hydrocarbons with unsaturated halides to produce higher boiling alkyl halides and hydrocarbons of higher molecular weight than the isoparaflins charged.

In one specific embodiment the present invention comprises a process for reacting isoparamnic hydrocarbons with halo-olefins in the presence of a metal halide catalyst of the Friedel-Crafts type.

Isobutane is the isoparafiln preferably subjected to reaction with a halo-olefin such as a chloro-olefin, bromo-olefln, etc., although higher molecular weight isoparafiins also react with such unsaturated halides to produce higher boiling alkyl halides or hydrocarbons of higher molecular weight than the isoparafiln charged. However, as the higher molecular weight isoparailins such as isopentane, isohexane, etc., are themselves valuable constituents of gasoline, they are consequently used less commonly than isobutane as charging stocks for conversion into higher molecular weight alkyl halides. Hydrocarbon mixtures containing substantial proportions of isoparaflins and normal parafllns are also utllizable in the process of this invention.

Halo-olefins which may be reacted or condensed with isoparaflins according to the process of the present invention contain at least one halogen atom per molecule and comprise haloethenes, -propenes, -butenes, -pentenes, and higher halo-alkenes. Vinyl chloride, allyl chloride, methallyl chloride, and the corresponding bromine compounds are representative of suitable halo-oleilns. The term halo-oleflns is also used herein in reference to other unsaturated compounds containing more than one halogen atom and more than one double bond per molecule. Halo-oleflns may be formed in any suitable manner such as by the action of a halogen upon an olefinic hydrocarbon at a temperature at which substitution occurs and substantially in excess of that at which addition of halogen to the oleflnic double bond is the principal reaction. They may also be prepared by the removal of one molecule of hydrogen halide from a dihalo-alkene by any of several well-known methods. I

Catalysts oi the Friedel-Craits type utilizable in effecting the interaction of a halo-olefin with an isoparaiiin include ,metal chlorides and bromides and particularly chlorides of aluminum aluminum chloride is generally more, widely applicable in that it possesses substantial catalytic activity at relatively low temperatures. Metal halides of the Friedel-Craft's type are employed as catalysts preferably at temperatures between about -30 and about +25 0., although higher temperatures, generally not in excess of about 100 C., are also sometimes utilizable with certain reaction mixtures comprising essentially isoparaflins and halo-olefins/ Metal halide catalysts of the Friedel-Crafts type may be employed as such, as mixtures, or supported by carriers such as alumina, diatomaceous earth, clay, pumice, activated charcoal, etc. The materials so utilizable as carriers should have substantially no harmful effect on the catalyst activity of the metal halide or mixture of metal halides employed.

While the reaction 01' an isoparaflin with a halo-olefin is not understood completely, it is believed that itinvolves the addition of .an isoparaffin to the double bond of the halo-olefin particularly at temperatures below about 0 C. Such an addition reaction apparently results in the formation of an alkyl halide of higher holling point than the reactants and with a molecular weight which is equal to the sum of the molecular weights of the reacting isoparaifin and unsaturated halide. At a higher reaction temperature it appears that an alkyl halide is first formed and then this compound undergoes an intra-molecular change or hydrogen disproportionation with the charged isoparafiin producing a higher boiling isoparaflin and liberating hydrogen halide. Thus, in runs in which allyl chloride was added gradually to a mixture of and zirconium. Of these catalytic materials,

ward the end of the period during which allyl chloride was introduced. In order to obtain high yields of alkyl halides a molar excess of isoparaflin to halo-olefin should be present throughout the entire reaction. Generally not more than about 20 molecular proportions of isoparaflin per molecular proportion of halo-olefin are present in the reaction-mixture charged to the process. I

Parailin formation, as mentioned above, probably occurred by way of intra-molecular hydrogen disproportionation between chloroheptane and isobutane. Reactions of this type are illustrated by the following equations:

chloride The isobutene thus formed according to the equation may then react with either aluminum chloride to form sludge-like material or with isobutane to form a parafiln fraction containing substantial amounts of iso-octan'e.

I have found that condensation of a monohaloolefin with an isoparafiin in the presence of a Friedel-Crafts type catalyst results not only in the formation of an alkyl halide but also that the reaction mixture usually contains dihalides having the same number of .carbon atoms per molecule as the monohaloalkane which is the major product of the reaction.

. The condensation of an isoparaflin with a haloolefln, unsaturated halide, or alkenyl halide of the type of vinyl-, allyl-, methallyl-chloride or -bromide, etc., is carried out using either batch or continuous operation. Thus, in batch type operation a halo-olefin is added gradually to a reactor containing an isoparaflln and a catalyst of the Friedel-Crafts type. The reaction temperature is maintained preferably between about -30 and about 25 C. and under suflicient pressure to keep in liquid state a substantial proportion of the reactants. The reaction mixture is also agitated by stirring, shaking, or some other suitable means to efiect intimate contact of the reactants and catalyst. During this treatment, the isoparaflln combines chemically with the halo-olefin to produce an alkyl halide with a molecular weight which is equal to the sum of the molecular weights of the reacting isoparafiin and halo-olefin. At higher temperatures, some of the alkyl halide may be converted into paraffinic hydrocarbons of gasoline boiling range, said hydrocarbons being the principal product of the process when the condensation reaction is carried out at a temperature of about 25 C. or higher in the presence of a catalyst of relatively high activity. At the higher rea'ction temperatures, hydrogen chloride is generally evolved from the reaction mixture. After such a batch type of operation, the normally liquid products are separated from the catalyst and the latter is returned to further use in the condensation reaction zone. Hydrogen halide present in the reaction products may be returned to the process or utilized for some other purpose as desired. In some cases it i desirable to commingle hydrogen with the reaction mixture since it has a tendency to increase the active life of the catalyst.

Continuous condensation of isoparaffin with a halo-olefin is carried out by introducing the haloolefin, also referred to as an unsaturated halide. or a mixture of an isoparafiln and said halide to a circulatin commingled mixture of an isoparaffin and a metal halide catalyst, particularly aluminum chloride or another compound of the Friedel-Crafts type. The mixture of isoparafiin, halo-olefin, catalyst, and sometimes, a ydrogen halide is directed through a tortuous path in some type of baffle mixer or through a reactor containing packing material to effect intimate contact of the catalyst with the reacting hydrocarbons. The conditions of temperature and pressure employed in such a condensation treatment are within the limits indicated above, but particular conditions used in any given condensation reaction vary with the molecular weights and reactivities of the reactants, the concentration and activity of the catalyst employed, and other factors.

The following examples are given to illustrate the character of the results obtained by the use of the present process, although the data presented are not introduced with the intention of unduly restricting the generally broad, scope of the invention.

EXAMPLE I Several runs indicated in Table 1 were made at the reflux temperature of the reaction mixture and at atmospheric pressure by introducing allyl chloride gradually to a well-stirred mixture of aluminum chloride and isobutane. In'the first of these runs it was found that-very little hydrogen chloride was evolved until about 40 grams of allyl chloride had been added to the mixture of 15 grams of aluminum chloride and 160 grams of isobutane. At this point, the catalyst had been converted from the original yellow powder into a tan colored semisolid material most of which collected on the walls of the reaction vessel. When more allyl chloride was added, a copious evoluation of hydrogen chloride occurred and the catalyst became more liquid in appearance and darker in color. Addition of allyl chloride was stopped after grams had been introduced to the reaction during a period of 2 hours but the stirring was continued for another hour during which time the evolution of hydrogen chloride increased. Evolution of hydrogen chloride was quite rapid at the end of the hour of stirring at which time the reaction product was separated from the catalyst layer. Distillation of the stabilized and washed liquid product showed that it had a wide boiling range with plateaus corresponding to hexane, heptane, and chloroheptane.

TABLE 1 Condensation of allyl chloride with isobutane Run No.

Reactants, .g'rams:

Isobutane L 202 195 380 350 365 Allyl chloride. 90 52 56 94 92 164 Aluminum chloride catalyst. 15 30 5 15 80 80 Products, grams:

Oondensible gas 74 172 325 277 12) Liquid product 137 78 70 135 161 284 Hydrogen chloride.... 17 l 3 4 8 63 Used catalyst 33 33 13 21 88 128 Loss 4 0 0 4 0 l4 Yields, weight percent of the allyl chloride c arged:

Liciuid paraflins 85 30 10 9 50 175 Ch oroheptane 30 70 40 60 68 0 Dichloroheptane 15 30 36 33 28 0 Higher-boiling chlorohydrocarbons 25 30 36 33 28 0 Catalyst weight increase 20 6 l4 6 9 29 In Run 2 shown in the table, the addition of allyl chloride was stopped as soon as an appreciable amount of hydrogen chloride began to be evolved, after which stirring was continued for 10 minutes. The liquid product was then decanted immediately from the yellow granular catalyst, stabilized, washed and distilled. when using this method or treatment a small amount of material was obtained boiling in the heptane range and a very large amount in the'chloroheptane range. There was very little intermediate product but evidence was available showing the presence 01' chloro-hexane. These results indicate that under the conditions shown chloroheptane is a primary product formed in the reaction of isobutane with allyl chloride in the presence of aluminum chloride.

Runs '3, 4, and 5 were made by reacting isobutane and allyl chloride in the presence of progressively larger amounts oi aluminum chloride as shown in Table 1. The formation of liquid, paraflins was greatest in the presence of the largest amount of catalyst and the producheptane occurred in Run in the presence of zirconium chloride.

Following essentially the same procedure used in Runs 8 and 9 of Example 11, the condensation of 45 grams of 2-chloro-propene with 380 grams ,of isobutane in the presence of grams of .as the result of condensation and reduction reactions.

The formation of tertiary butyl chloride during the reaction of 2-chloroprcpene with isobution of chloroheptane and dichloroheptane was also considerable.

Run 6 in which more allyl chloride was charged than than introduced in Run 5, but with the sameamount of aluminum chloride catalyst, yielded a, reaction product consisting almost entirely of liquid parafilnic hydrocarbons. The catalyst also increased in weight more than did the catalysts employed in the other runs to which less allyl chloride was charged. I

EXAMPLE II In each of a number of runs, 380 grams 0! isobutane and aluminum chloride or zirconium chloride in the amounts shown in Table 2 were contacted with 82 grams oi allyl chloride, the

'latter being introduced slowly to the reactor during a period of 1 to 2 hours, while the reaction, mixture was stirred and maintained at temperatures between about 40 and +50 C.

- Runs 8 and 9 were carried out under atmospheric pressurein a glass vessel providedwith a stirrer, but each of-the other runs was made in a rotatable steel autoclave under the vapor pressure of the reaction mixture. At temperatures below about C. the allyl chloride was recovered unchanged, while in similar operations but at -25 C. chloroheptane and other chlorinated hydrocarbons wereobtained. At higher temperatures and particularly at +20 to 0., parafflnic hydrocarbons constituted uct oi the process.

Tans: 2 Condensation'bf allyl chloride with isobutane tane was believed to indicate the intermediate formation or isobuten'e which then could react the main prod- Run Weight I Catalyst oi Tem Products catalyst I p Grams '0. 8 AlCh." 20 35 All lchloride recovered. 9 A101,"- 20 26 Ch oroheptane and other chloriiecontaining comun s. 11 M011". 6 +24 C ieiiy parailins with some chlornheptane. 12 AlCh.-- 15 20 Paraflins. 13..." A101; 15 30 Do. 15 ZrCh 2Q 28 Chloroheptane and other chlorine-containing oompounds. l6 ZrCh 2D 60 Relatively high boiling hyv drocarbons.

As indicated by Runs 15 and 16 in Table 2. zirconium chloride catalyzed the condensation of allyl chloride with isobutane at room temperature to form substantially the same chloro-compounds which were obtained in the presence of aluminum chloride at a lower temperature. Very little reduction of the chloro-compounds to with hydrogen chloride to produce tertiary butyl chloride. EXAMPLE IV tanes)- and chloro-octane.

EXAMPLE v A hexane traction, tertiary butyl chloride, and

a chloro-compound (apparently CsHuCh) boiling at 146 to 148 C. were the chief products formed by reacting isobutane with vinyl chloride in the presence of aluminum chloride at l0 and +23 C. *No reaction occurred when isobutane, vinyl chloride, and aluminum chloride were contacted for 1 hour at 25 C. The results obtained in 4 runs made at these diflerent temperatures are shown in Table 3.

Tssu: 3 I Condensation of vinyl chloride with isobutane Run No.

Reactants, grams:

Isobutane 383 Vinyl chloride 96 32 Aluminum chloride catalyst 20 20 8 Time, hours l 3 4 Temperature, "C 26 -ll 25 Products grams:

Condensible gas an 453 271 23 Liquid product... 121 0 123 61 Catalyst layer 31 27 42 22 Hydrogen chloride 6 0 2 7 v 11 1s 2s 7 Distillation of liquid product, vol. percent:

Below 20 C"... 22 34 66 C 11 5 8 l7 Condensible gas from Run 2. Bath temperature was -30 C. (durin 1.5 hours) allowed to rise to at which'temperature In this way methallyl chloride was 7 isobutane occurred at 28-25 C. in the presence or aluminum chloride, yielding hexanes, octanes,

and a chloro-compound boiling between 196 and 200 C. and melting at about 16 C. Th results obtained in two runs are shown in Table 4.

TABLI 4 Condensation of dichloro-ethylerw with. isobutane Temperature, C 23 24 Time rotation of autoclave, hours--- 4 4 Reactants, grams:

Isobutane 4'1 122 Dichloro-ethylene 20 50 Aluminum chloride catalyst 5 l0 Products, grams:

Unconverted isobutane 20 48 Liquid product. 28 93 Used catalyst 28 Hydrogen chloride 5 11 Loss 4 2 Distillation of liquid product, vol. per cent: Fraction boiling- Below 50 8 6 50-75 ..n., 13, 9 75-95 6 2 95-125 8 8 125-1'75' '7 3 175-200 25 25. Residue 8 8 The novelty and utility of the process of the present invention are evident from the preceding specification and examples, although neither section is intended to unduly limit its generally broad scope.

I claim as my invention:

1. A process which comprises reacting an isoparamnic hydrocarbon with a halo-olefin in the presence of a metal halide catalyst.

2. A process which comprises reacting an isoparaflinic hydrocarbon with a halo-olefin in the presence oi a metal halide catalyst'oi the Friedel- Craits type. q

3; A process which paraiiinic hydrocarbon with a halo-olefin in the essence under suiiicient pressure to keep in liquid state a substantial proportion oi the reaction mixture.

8. The process of claim 8 further characterized in that said halo-olefin comprises a chloro- 9. The process of, claim 6 further characterized in that said relatively low boiling isoparamnic hydrocarbon comprises isobutane.

10. The process of claim 6 iurther characterized in that said relatively low boiling isoparaflnic hydrocarbon comprises isopentane.

11. A process which comprises reacting an isoparaiiinic hydrocarbon with a halo-olefin in the presence of an aluminum halide catalyst.

12. A process which comprises reacting an isoparamnic hydrocarbon with a mono chloro-olenn in the presence of an aluminum chloride catalyst.

13. A process which comprises reacting an isoparamnic hydrocarbon with a chloro-oleiln in the presence of an aluminum chloride catalyst at aootemperature of from about '80" to about 1 C.

14. A process which comprises reacting an isoparaiiinic hydrocarbon with a chloro-olefln in the presence of an aluminum chloride catalystat a temperature of from about -80 to about 100 C. under sumcient pressure to keep in liquid state a substantial proportion oi the reaction mixture.

15. A. process which comprises reacting isobutane with a chloro-oleiin in" the prsence of an aluminum chloride cats t at a temperature of from about --30 to abo t 100' C. under suiflcient pressure to keep in liquid state a substantial proportion of the reaction mixture.

16. A process which comprises reacting isopentane with a chloro-olefln in the presence of an aluminum chloride catalyst at a temperature comprises reacting an isopresence of'a metal halide catalyst of the Friedel- Crafts type at a temperature oi from about 30 to about 100 C.

4. A process which comprises reacting an isoparamnic hydrocarbon with a halo-olefin in the presence of a metal halide catalyst of the Friedei-.

Craits type at a temperatureoi' from about 80 to about 100 C. under suiiicient pressure to keep in liquid state a substantial proportion oi the reaction mixture. q

5. A process which comprises reacting a relatively low boiling isoparai'iinic hydrocarbon with a mono-halo-oleiin in the presence of a metal halide catalyst-pi, the Friedel-Orafts type.

6. A process which .comprises reacting-a relatively low boiling isoparamnic hydrocarbon with a halo-olefin in the presence or a metal halide catalyst of the Friedel-Craitstype at atemperature oi from about -80 to about 100' C.-

7. A process which comprises reacting a relatively low boiling isoparaiiinic hydrocarbon with a halo-olefin in the presence of a metal halide catalyst of the model-Crafts type at a temper-,-

ature of from about 80 to about +100" 0..

or from about to about C. under suincient pressure to keep in liquid state a substantial proportion 01' the reaction mixture.

17. A process which comprises reacting isobutane with a halo-ethane in the presence oi an aluminum chloride catalyst at a temperature of from about -SO to about 100' C. under suiflcient pressure to keep in liquid state a substantial proportion of the reaction mixture.

18. A process which comprises reacting isobutime with a mono chloropropene in presence 01' an aluminum chloride catalyst at a temperstars of from about 80 to about 100 C. under suiiicient pressure to keep in liquid state a substantial proportion of the reaction mixture.

19. A process which comprises reacting isobutane with a mono chloro-butene in the presence oi-an aluminum chloride catalyst at a temperature of from about .-80 to about 100 C. under sumcient pressure to keep 'in liquid state a substantial proportion of the reaction mixture.

20. A process which comprises reacting isobutane with allyl chloride in the presence or an aluminum chloride catalyst at a temperature of w from about .30 to about 100 C. under sui' flcient pressure to keep in liquid state a substan tiai proportion oi the reaction mixture. 1 21 A process which comprises reacting-isobu, tans with dichloroethylene in the presence of an aluminum chloride catalyst at a temperature of from about -30 C. to about 100' C. under suincient pressure to maintain a substantial portion of'thereactantsinliqiudphase.

' LOUIS BOWLING. 

